The Brazilian had little joy in the opening moments at the Parc des Princes.
But Neymar – a reported transfer target for Barcelona and Real Madrid – would change his boots.
And just moments later he put Paris Saint-Germain 2-0 up against the Reds.
That was following the opener from Juan Bernat in the 13th minute.
But Liverpool did pull one back thanks to a James Milner penalty.
Sadio Mane was brought down in the box by former Manchester United winger Angel di Maria.
The referee initially gave a corner but after advice from the official behind the goal he awarded the spot kick.
And PSG midfielder Marco Verratti could have easily been sent off for a poor challenge on Joe Gomez as well.
Neymar will hope to get on the scoresheet again in the second half as PSG look to progress to the last 16.
The other match in Champions League Group C sees Napoli take on Red Star Belgrade.
At half-time the Italian side were 2-0 up which piles the pressure on Liverpool.
Jurgen Klopp’s men would be third on six points going into their final match if results stayed as they are.
Next up for Liverpool in the Champions League is Napoli at Anfield on December 11.
Before that the Reds face Premier League matches against Everton, Burnley and Bournemouth.
Klopp will be hopeful his side can turn things around and get something from the match against PSG in the second half.